CN101518259B - Antibacterial application of polycrystalline nanometer calcium-aluminum oxide - Google Patents
Antibacterial application of polycrystalline nanometer calcium-aluminum oxide Download PDFInfo
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- CN101518259B CN101518259B CN200910116326XA CN200910116326A CN101518259B CN 101518259 B CN101518259 B CN 101518259B CN 200910116326X A CN200910116326X A CN 200910116326XA CN 200910116326 A CN200910116326 A CN 200910116326A CN 101518259 B CN101518259 B CN 101518259B
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Abstract
The present invention relates to an inorganic antibacterial material, in particular to an antibacterial application of a polycrystalline nanometer calcium-aluminum oxide of C12A7-O<->. The antibacterial material has broad-spectrum bacteriostatic and bactericidal actions, i.e. has the action for exterminating golden staphylococcus, colon bacilli and hay bacillus black spore varieties at a room temperature. The polycrystalline nanometer calcium-aluminum oxide has an extermination rate of 100 percent per hour for the golden staphylococcus and the colon bacilli and has an extermination rate of 96 percent per hour for the hay bacillus black spore varieties when a load weight on a unit area of a load material is heavier than or equal to 0.005g/cm<2> the grain diameter of the polycrystalline nanometer calcium-aluminum oxide is 10- 200nm, the load material can be textile, plastic products, ceramics, rubber products, or the like, and the room temperature means natural room-temperature conditions in four seasons. The polycrystalline nanometer calcium-aluminum oxide has the advantages of strong antibacterium function, no toxicity, high temperature resistance and strong stability and can be widely applied to fields, such as antibacterial textile, antibacterial plastics or ceramics, rubber products, and the like.
Description
Technical field
The present invention relates to inorganic antibacterial material, be specifically related to a kind of polycrystal nano calcium aluminum oxide C12A7-O
-Material is used for the purposes of kill bacteria aspect.
Background technology
Bacterium and virus are followed among the development of human society all the time.In the past few decades, owing to the increase of population and the reasons such as destruction of ecotope, the disease of originally having controlled and the pathogene of variation are deepened day by day to the human health influence degree, for example, tubercle bacillus (Mycobacterium Tuberculosis), the coronavirus of atypical pneumonia (SARS), H5N1 type avian influenza virus etc., up to now, large-scale communicable disease eruption and prevalence has taken place repeatedly in the whole world, has greatly influenced human normal economic life order and health.The relevant report of the World Health Organization shows have 3/4ths directly to come from the germ virus infections in the annual death toll in the whole world, has every year 1700 ten thousand people to die from infectious disease approximately in developing country.Therefore in the modern life, how purifying air, isolate, block the propagation of pathogenic microorganisms such as each viroids and bacterium, keep human living and living environment cleaning, all is urgent problem.Specifically as the filtration of various bacteriums in the air and virus, public and sterilization and all kinds of safe and sanitary hidden danger home environment all are current significant problems.In the long-term struggle of human and bacteriosis, it has been recognized that antibiotic importance.Beginning also progressively adopts anti-biotic material as prophylactic important measures in the small stores and the tool of production not only in hospital and public place.
The used anti-biotic material of people mainly is divided into inorganic antibacterial material and organic anti-bacterial material two big classes at present.The organic anti-bacterial material is meant various bacteria removers, bactericide etc., be generally the synthetic material of chemical substances such as organic acid, alcohol, ester, phenol, they have short-term sterilization result efficiently, but there is defective at aspects such as safety, broad spectrum activity, pesticide resistance and heat-resisting processabilities, its poor chemical stability, timeliness is short, the product of pyrolytic is poisonous, be difficult for merging with fungi-proofing object, be difficult to realize long-term antibiotic function, therefore be difficult to be applied in the goods such as coating, plastics, chemical fibre, pottery, rubber.Inorganic antibacterial material be with inorganic antiseptic support that some specific surface areas are big, the inorganic material surface of porous, good dispersion and the solid material made with antibiotic property, have broad spectrum antibacterial, water-fast, acid and alkali-resistance, wash resistant, do not wear out, do not develop immunity to drugs, characteristics such as antibacterial ability is lasting, more and more be subject to people's attention, can satisfy the requirement that people's life comfort level and health level improve constantly, begin to obtain application in fields such as building materials, ceramic sanitary appliance, plastics, textiles.
The existing inorganic antibacterial material of having studied can be divided into 3 classes: (1) metal ion type; (2) oxide catalytic type; (3) compound, its antibiotic mode is mainly two classes: a class is to be the contact sterilization of representative with silver ion etc., as United States Patent (USP) 6,379,712B1 discloses and provides a kind of granula manufacture method that contains the antibacterium and the fungi of nanometer silver granuel, United States Patent (USP) 6,482,424 is open and provide a kind of and have that to be covered with the copper cation be the medical treatment fabric fibre of oxidant.The preparation method of metal ion type antibacterial agent is earlier with antibiotic property metal ion Ag
+, Cu
2+Plasma, or the silicate, phosphate etc. that contain these ions are attached to making antibacterial agent on the carriers such as zeolite, silica gel, glass, again antibacterial agent is added in the goods raw material and make antibacterial product, but metal ions such as silver are strong to the reaction sensibility of light, oxidation easily, limited application, in addition, the cost of ionization series antibacterial agent is very high.What the application of second class was wider is with TiO
2Photocatalysis formula sterilization for representative.Be used for as what Chinese patent 200410010782.3 disclosed a kind of excited by visible light that indoor-outdoor air purifies and the composite photocatalyst anti-biotic material of sterilization, Chinese patent 200710068140.2 discloses a kind of light catalytic waste water processing device.Its sterilization mechanism is in photocatalysis antibacterial agent semi-conductor type compound, optical excitation makes the electron transition that is positioned at valence band to conduction band, the electronics that is excited in the conduction band has strong reducing power, hole in the valence band has strong oxidability, but so killing bacteria, really play functions such as self-cleaning, sterilization, deodorizing.But its shortcoming also is conspicuous, and photocatalysis characteristic mainly needs ultraviolet source, and low to the availability of visible light, photocatalysis efficiency is low, is not easy in indoor use.Second kind of the metal oxide oxidation catalyst type is nano-metal-oxide, as Chinese patent 200410010782.3 disclose a kind of by silicate-base mano-porous material and nano zinc oxide particles, zinc ion preparation silicate zinc oxide particle nano composite material and this material in the application aspect antibacterial and the sterilization.Chinese patent 200410029592.6 discloses a kind of loaded nano magnesia, and magnesia is carried on alumina surface, makes it in the alumina surface high degree of dispersion, as sterilization material.But magnesium, zinc are not a large amount of elements that exist in the human body, are extensive use of to contact with human body, may cause damage to body.
C12A7 is a kind of nanoscale cage shape crystalline material, and a mayenite structure cell contains two C12A7 molecules, by [a Ca
24Al
28O
64]
4+Dot matrix framework and two O
2-Ion is formed, and the dot matrix framework of positively charged forms the cage that 12 diameters are about 0.4nm.C12A7 used the solid phase synthesis process artificial preparation to form (document: G.A.Rankin, and F.E.Wright, Ameriean Journal of Science, 39,1 (1915)) by Rankin and Wright in 1915 first.Studies show that the free oxonium ion (O in the free C12A7 cage recently
2-) can be by other anion (as O
-, H
-, OH
-, F
-, Cl
-Anion and electronics e
-) part replaces, and then synthetic various C12A7 derivatives of different nature, these C12A7 derivatives are with a wide range of applications, as by O
-The C12A7 derivative that replaces (is labeled as C12A7-O
-) can be used for making high-purity O
-Negative ion source (document: Quanxin Li, etc.Surface Science, 527,100-112 (2003)), this high-purity O
-Negative ion source can be used for studying O
-Microorganism deactivated (document: Wang Lian etc., biochemistry and biophysics progress, 34 (12) that anion is induced, 1288-1295 (2007)) and modifying surface of polymer material (document: LianWang, etc.Applied Surface Science, 254,4191-4200 (2008)); By H
-The C12A7 derivative that replaces (is labeled as C12A7-H
-) can be used for making optical semiconductor material (document: KatsuroHayashi, etc.Nature, 419,462-465 (2002)); By e
-The C12A7 derivative that replaces (is labeled as C12A7-e
-) can be used for making room temperature oxide electrode and cold electronic field emission device (document: Masashi Miyakawa, etc.Advanced Materials, 15,1100-1103 (2003)); By F
-The C12A7 derivative that replaces (is labeled as C12A7-F
-) can be used for making high-purity F
-Negative ion source and conductor etching (document: Chongfu Song, etc.Chemistry ofMaterials, 20,3473-3479 (2008)).The preparation method of existing C 12A7 and derivative thereof utilizes CaCO
3And γ-Al
2O
3(as oxygen, hydrogen, fluorine gas etc.) and synthetic making under the high-temperature roasting condition more than 1350 ℃ in different atmosphere, synthesis condition harshness (as needs 200-300atm compressing tablet, high-temperature roasting more than 1350 ℃) often comprises simultaneously other impurity (as C5A3 etc.) in the synthetic sample; In addition, find no up to now C12A7 and derivative thereof aspect report as anti-biotic material.
Summary of the invention
The objective of the invention is to, polycrystal nano calcium aluminum oxide C12A7-O is provided
-＜its chemical expression is [Ca
24Al
28O
64]
4+(O
-)
x(O
2 -)
y(O
2-)
zAs the new purposes of anti-biotic material aspect.
Purpose of the present invention is achieved through the following technical solutions.
Polycrystal nano calcium aluminum oxide C12A7-O of the present invention
-Purposes as anti-biotic material, it is characterized in that, this anti-biotic material has broad-spectrum antibacterial and bactericidal action, described broad-spectrum antibacterial and sterilization are meant has killing action to staphylococcus aureus, colon bacillus, bacillus subtilis black variety gemma in normal temperature, load weight is more than or equal to 0.005g/cm on the unit are of polycrystal nano calcium aluminum oxide in support materials
2The time, be 100% to staphylococcus aureus, 1 hour killing rate of colon bacillus, be more than 96% to 1 hour killing rate of bacillus subtilis black variety gemma effect; Load weight is 0.0025g/cm on the unit are of polycrystal nano calcium aluminum oxide in support materials
2-0.005g/cm
2The time, be 99-100% to staphylococcus aureus, 1 hour killing rate of colon bacillus effect, be 91-96% to 1 hour killing rate of bacillus subtilis black variety gemma effect; Load weight is 0.0005g/cm on the unit are of polycrystal nano calcium aluminum oxide in support materials
2-0.0025g/cm
2The time, be 98-99% to 1 hour killing rate of staphylococcus aureus effect, be 84-99% to 1 hour killing rate of colon bacillus effect, be 29-91% to 1 hour killing rate of bacillus subtilis black variety gemma effect; The particle diameter of wherein said polycrystal nano calcium aluminum oxide is 10～200nm.Described support materials is textile or plastic products or pottery, rubber etc.; Described normal temperature is meant natural room temperature condition in the four seasons.
Described polycrystal nano calcium aluminum oxide is carried on miillpore filter or the textile even load material staphylococcus aureus, colon bacillus, bacillus subtilis black variety gemma are carried out normal temperature dry type sterilization experiment.Experimental procedure is as follows: take by weighing a certain amount of polycrystal nano calcium aluminum oxide powder, carry out sterilization treatment 5h at 120 ℃, polycrystal nano calcium aluminum oxide powder after the sterilization is placed miillpore filter (for example mixed cellulose ester microporous membrane) surface that is coated with staphylococcus aureus, colon bacillus, bacillus subtilis black variety gemma respectively, and three kinds of bacteria containing amounts of this filter membrane are 10
6-10
9Cfu/mL.After the sterilization at normal temperatures a hour, be flushed in the centrifuge tube with the whole bacteriums and the polycrystal nano calcium aluminum oxide powder sample of sterile distilled water film surface, with sample in the physiological saline vibration flushing centrifuge tube, after room temperature leaves standstill 15min, get supernatant solution and be inoculated into nutrient agar (peptone 10g/l, beef extract 3g/l, sodium chloride 5g/l, agar 15g/l, pH 7.2) on the medium, be put into then and behind incubator 24h, carry out count plate, and with Al
2O
3Sample is contrast, calculates killing rate.
Actual measurement shows, when the load capacity of described polycrystal nano calcium aluminum oxide on support materials is 0.0025g/cm
2The time, it is 99% to staphylococcus aureus, 1 hour killing rate of colon bacillus effect, is 91% to 1 hour killing rate of bacillus subtilis black variety gemma effect; When the load capacity of described polycrystal nano calcium aluminum oxide is 0.005g/cm
2The time, it has reached 100% to staphylococcus aureus, colon bacillus killing rate, and the killing rate of bacillus subtilis black variety gemma has been reached 96%, has satisfied fully as the requirement of sterilization material fast and effectively.
Polycrystal nano calcium aluminum oxide C12A7-O
-Be the white solid powder, have very strong antibacterial functions, and nontoxic, high temperature resistant, stable strong, therefore can be widely used in antibacterial fabric, antibiotic plastic or fields such as pottery, rubber.In actual applications, can select to use different load capacity according to different use occasions or needs.
Described polycrystal nano calcium aluminum oxide can use traditional solid phase synthesis process preparation: promptly utilize CaCO
3And γ-Al
2O
3Powder is a raw material, under the 200-300atm condition, carry out the compressing tablet processing to mixing the back powder, then with the synthetic method of sample behind the compressing tablet in high-temperature roasting more than 1350 ℃, the method in document described in the above-mentioned background technology " Surface Science ", narrated of people such as Li Quanxin for example.
Described polycrystal nano calcium aluminum oxide also can be obtained by following method:
In concentration is in the aqueous citric acid solution of 0.2-0.3g/ml, adds nitrate of lime (Ca (NO
3)
24H
2O) (purity: analyze pure) and aluminum nitrate (Al (NO
3)
39H
2O) (purity: analyze pure), wherein nitrate of lime is 28.34/52.52 (the corresponding nitrate of lime and the mol ratio of aluminum nitrate are 12/14) with the mass ratio of aluminum nitrate, the quality of nitrate of lime is 0.01-0.12g/ml with the ratio of aqueous citric acid solution volume; Add polyglycol surfactants (purity: analyze pure) then, the quality of polyethylene glycol is 2.5mg/ml with the ratio of aqueous citric acid solution volume; The control bath temperature obtains settled solution with the rotating speed continuous stirring of 200-500r/min until dissolving under 70-80 ℃ of condition;
Add ethylene glycol (purity: analyze pure) in above-mentioned solution, the addition of ethylene glycol is 0.25-0.6/1 with the ratio of the volume of aqueous citric acid solution; , in 90 ℃ of environment, leave standstill then and formed calcium aluminium salt gel in 24 hours until forming calcium aluminium salt sol with the rotating speed continuous stirring of 200-500r/min; Calcium aluminium salt gel is heated to 350-400 ℃ and be incubated 1-2 hour in air atmosphere, makes it form blocks of solid; Blocks of solid is ground to form the particulate of particle diameter less than 0.15mm; Place uncovered quartz or ceramic vessel to put in the sealed reactor particulate after grinding, the feeding flow velocity is 50-100cm again
3The oxygen of/min is under the condition of 0.11-0.13MPa at oxygen atmosphere pressure, is heated to 900-1150 ℃ and be incubated 8-10 hour with 5-10 ℃ of/minute programming rate, and obtaining particle diameter is the polycrystal nano calcium aluminum oxide (C12A7-O of 10-200nm
-).
Embodiment
Be described further by the following examples.
Embodiment 1 preparation polycrystal nano calcium aluminum oxide
In 200ml concentration is in the aqueous citric acid solution of 0.2g/ml, adds 2.48g nitrate of lime (Ca (NO
3)
24H
2O) (purity: analyze pure) and 4.60g aluminum nitrate (Al (NO
3)
39H
2O) (purity: analyze pure) adds 0.5g polyglycol surfactants (purity: analyze pure) then, controls bath temperature at 70 ℃, and obtains settled solution with the rotating speed continuous stirring of 200r/min until dissolving;
In solution, add 50ml ethylene glycol (purity: analyzes pure), with the rotating speed continuous stirring of 200r/min 2 hours, formation calcium aluminium salt sol; 90 ℃ leave standstill 24 hours formation calcium aluminium salt gels; Calcium aluminium salt gel is heated to 350 ℃ and be incubated 2 hours in air atmosphere, forms block solid; The solid abrasive of bulk is become the particulate of particle diameter less than 0.15mm; Place uncovered quartz container to put in the sealed reactor particulate after grinding, the feeding flow velocity is 50-100cm again
3The oxygen of/min is 0.11-0.13MPa at oxygen atmosphere pressure, is heated to 1150 ℃ and be incubated 10 hours with 10 ℃ of/minute programming rates, and obtaining particle diameter is the polycrystalline calcium aluminum oxide (C12A7-O of 65nm ± 30nm
-).
Embodiment 2 preparation polycrystal nano calcium aluminum oxides
In 200ml concentration is in the aqueous citric acid solution of 0.2g/ml, adds 24.80g nitrate of lime (Ca (NO
3)
24H
2O) (purity: analyze pure) and 45.95g aluminum nitrate (Al (NO
3)
39H
2O) (purity: analyze pure) adds 0.5g polyglycol surfactants (purity: analyze pure) then, controls bath temperature at 80 ℃, and obtains settled solution with the rotating speed continuous stirring of 500r/min until dissolving; In settled solution, add 120ml ethylene glycol (purity: analyzes pure), with the rotating speed continuous stirring of 500r/min 2 hours, formation calcium aluminium salt sol; 90 ℃ leave standstill 24 hours formation calcium aluminium salt gels; Calcium aluminium salt gel is heated to 400 ℃ and be incubated 1 hour in air atmosphere, forms block solid; The solid abrasive of bulk is become the particulate of particle diameter less than 0.15mm, place uncovered quartz container to put in the sealed reactor particulate after grinding again, the feeding flow velocity is 50-100cm
3The oxygen of/min is under the 0.11-0.13MPa condition at oxygen atmosphere pressure, is heated to 900 ℃ and be incubated 10 hours with 10 ℃ of/minute programming rates, and obtaining particle diameter is the calcium aluminum oxide (C12A7-O of 35nm ± 15nm
-).
Embodiment 3 test implementation examples 2 samples are to the killing effect of staphylococcus aureus
(1) take by weighing the polycrystalline calcium aluminum oxide powder sample of the 35nm ± 15nm of embodiment 2 preparation, it is standby to carry out sterilization treatment 5h at 120 ℃;
(2) mixed cellulose ester microporous membrane (is gone up Haixing County inferior scavenging material factory, specification: φ 50mm, aperture: 0.45 μ m) place the culture dish that is covered with discolour silica gel, carry out sterilization treatment after 5 hours at 120 ℃, get with 6 of homalographics standby;
(3) will be seeded in staphylococcus aureus on the nutrient agar plate (Chinese common micro-organisms culture presevation administrative center provide) with aseptic inoculation shovel draws gently and falls, add the 5ml stroke-physiological saline solution, with aseptic micropipettor the sucking-off of bacterium liquid is added in the centrifuge tube again, be put into centrifugal 5min in the centrifuge (4000rpm) then, obtain pure bacterium liquid, it is 10 that gained bacterium liquid is diluted to bacteria containing amount with physiological saline
8Cfu/ml is standby;
(4) (bacteria containing amount is 10 to the bacterium liquid that above-mentioned 500 μ l are diluted
8Cfu/ml) evenly cover on six mixed cellulose ester microporous membranes dry 30min under the room temperature;
(5) to be divided into load capacity be 0.0005g/cm to the polycrystal nano calcium aluminum oxide powder after will sterilizing
2, 0.0025g/cm
2, 0.005g/cm
2Three groups (two parts every group) evenly place six parts of mixed cellulose ester microporous membrane surfaces that are coated with staphylococcus aureus, act on 30 minutes respectively and 1 hour under 37 ℃ of room temperatures;
(6) wash whole bacteriums and the polycrystal nano calcium aluminum oxide powder sample of transferring to the filter membrane surface in the centrifuge tube with the physiological saline vibration respectively, after room temperature leaves standstill 15min, get supernatant solution and be inoculated into nutrient agar (peptone 10g/l, beef extract 3g/l, sodium chloride 5g/l, agar 15g/l, pH 7.2) on the medium, be put into then and carry out count plate after in insulating box, cultivating 24h;
(7) use Al
2O
3Test in contrast powder sample (available from Chemical Reagent Co., Ltd., Sinopharm Group) repeating step (1)-(6), calculates killing rate.
In the present embodiment process, measurement result is as shown in table 1 under the load capacity of different polycrystal nano calcium aluminum oxides (weight that contains polycrystal nano calcium aluminum oxide on the mixed cellulose ester microporous membrane unit are) and different action times.Can find out from this table: when the load capacity of described polycrystal nano calcium aluminum oxide at 0.0005g/cm
2The time, its killing rate to staphylococcus aureus effect 30min and 1h is respectively 92.96% and 98.61%; When the load capacity of described polycrystal nano calcium aluminum oxide at 0.005g/cm
2The time, its killing rate to staphylococcus aureus effect 30min and 1h is 100%, shows that the load capacity of working as described polycrystal nano calcium aluminum oxide is at 0.0005-0.005g/cm
2The time, it has bactericidal action fast and effectively to staphylococcus aureus.In contrast, give Al in the table
2O
3The test result of powder.Work as Al
2O
3The load capacity of powder is at 0.005g/cm
2The time, its killing rate to staphylococcus aureus effect 30min and 1h is respectively 0 and 22.63%.Positive control in the table is meant the situation that does not apply any anti-biotic material.
Table 1 different loads amount polycrystal nano calcium aluminum oxide is to staphylococcus aureus exercising result (data are the mean value of three experiments in the table)
Embodiment 4 test implementation examples 1 sample is to the killing effect of colon bacillus
The present embodiment process is with embodiment 3, and used bacterial classification changes colon bacillus into.Measurement result is as shown in table 2 under the load capacity of different polycrystal nano calcium aluminum oxides and different action times.Can find out from this table: when the load capacity of described polycrystal nano calcium aluminum oxide at 0.0025g/cm
2The time, its to the killing rate of colon bacillus effect 30min and 1h all greater than 99%; When the load capacity of described polycrystal nano calcium aluminum oxide anti-biotic material at 0.005g/cm
2The time, its killing rate to colon bacillus effect 30min and 1h is 100%, shows that the load capacity of working as described polycrystal nano calcium aluminum oxide is at 0.0025-0.005g/cm
2The time, it has bactericidal action fast and effectively to colon bacillus.In contrast, work as Al
2O
3The load capacity of powder is at 0.005g/cm
2The time, its killing rate to colon bacillus effect 30min and 1h is respectively 25.72% and 25.64%.Positive control in the table is meant the situation that does not apply anti-biotic material.
Table 2 different loads amount polycrystal nano calcium aluminum oxide and colon bacillus exercising result (data are the mean value of three experiments in the table)
Embodiment 5 test implementation examples 1 sample is to the killing effect of bacillus subtilis black variety gemma
In the present embodiment process, used bacterial classification changes homemade bacillus subtilis black variety gemma liquid into, and all the other are with embodiment 3.Use homemade bacillus subtilis black variety gemma liquid, measurement result is as shown in table 3 under the load capacity of different polycrystal nano calcium aluminum oxide anti-biotic materials and different action times.Can find out from this table: when the load capacity of described polycrystal nano calcium aluminum oxide anti-biotic material at 0.0025g/cm
2The time, its killing rate to bacillus subtilis black variety gemma effect 1h is 91.76%; When the load capacity of described polycrystal nano calcium aluminum oxide anti-biotic material at 0.005g/cm
2The time, its killing rate to bacillus subtilis black variety gemma effect 1h is 96.98%, shows that the load capacity of working as described polycrystal nano calcium aluminum oxide anti-biotic material is at 0.0025-0.005g/cm
2The time, it has bactericidal action fast and effectively to bacillus subtilis black variety gemma.In contrast, work as Al
2O
3The load capacity of powder is at 0.005g/cm
2The time, its killing rate to bacillus subtilis black variety gemma effect 30min and 1h is respectively 11.66 and 31.88%.Positive control in the table is meant the situation that does not apply anti-biotic material.
Table 3 different loads amount polycrystal nano calcium aluminum oxide and bacillus subtilis black variety gemma exercising result (data are the mean value of three experiments in the table)
Embodiment 6 test implementation examples 1 sample is carried on the killing effect of textile to staphylococcus aureus
(1) the gauze health gauze mask (Tongcheng City, Anhui Province green grass three field Sanitary Materials Factory products) of 32 * 2 centimetres of clips is put into absolute ethyl alcohol, add the 0.05g polycrystal nano calcium aluminum oxide powder sample that takes by weighing, after ultrasonic 1 hour (polycrystal nano calcium aluminum oxide powder load capacity on the unit are of every gauze health gauze mask is about 0.003g), carrying out hot air sterilization at 120 ℃ of drying boxes, to handle 5h standby;
(2) will be seeded in staphylococcus aureus on the nutrient agar plate (Chinese common micro-organisms culture presevation administrative center provide) with aseptic inoculation shovel draws gently and falls, add the 5ml stroke-physiological saline solution, be added in the centrifuge tube with the sucking-off of aseptic micropipette small of the stock bacterium liquid again, be put into centrifugal 5min in the centrifuge (4000rpm) then, obtain pure bacterium liquid, it is 10 that gained bacterium liquid is diluted to bacteria containing amount with physiological saline
8Cfu/ml is standby;
(3) (bacteria containing amount is 10 to the bacterium liquid that 200 μ l are diluted
8Cfu/ml) join on the gauze that respectively is loaded with sample powder of (1), effect is 1 hour under 10 ℃ room temperature.
(4) transfer to whole bacteriums and nanometer calcium aluminum oxide powder sample on the gauze in the centrifuge tube with physiological saline vibration flushing respectively, after room temperature leaves standstill 15min, be inoculated into nutrient agar (peptone 10g/l after getting the supernatant solution dilution, beef extract 3g/l, sodium chloride 5g/l, agar 15g/l, pH 7.2) on the medium, be put into then and carry out count plate after in insulating box, cultivating 24h; Calculate average kill ratio.
In the present embodiment process, the experimental result that polycrystal nano calcium aluminum oxide loads in the textile gauze is as shown in table 4.Can find out from this table: when ultrasonic 1 hour of described polycrystal nano calcium aluminum oxide loads on the textile cotton cloth respirator, 10 ℃ is 99.89% to 1 hour killing rate of staphylococcus aureus effect, shows that load has the textile of polycrystal nano calcium aluminum oxide that staphylococcus aureus is had bactericidal action fast and effectively.Common cotton cloth respirator in the table is meant that not load has the situation of nanometer calcium aluminum oxide powder.
Table 4 load has the cotton cloth respirator of polycrystal nano calcium aluminum oxide to staphylococcus aureus exercising result (data are the mean value of three experiments in the table)
Claims (4)
1. polycrystal nano calcium aluminum oxide C12A7-O
-Purposes as anti-biotic material, it is characterized in that, this anti-biotic material has broad-spectrum antibacterial and bactericidal action, described broad-spectrum antibacterial and sterilization are meant has killing action to staphylococcus aureus, colon bacillus, bacillus subtilis black variety gemma in normal temperature, the particle diameter of wherein said polycrystal nano calcium aluminum oxide is 10～200nm; Described support materials is textile or plastic products or pottery, rubber; Described normal temperature is meant natural room temperature condition in the four seasons; Described polycrystal nano calcium aluminum oxide C12A7-O
-Obtained by following method: in concentration is in the aqueous citric acid solution of 0.2-0.3g/ml, add nitrate of lime and aluminum nitrate, wherein the mass ratio of nitrate of lime and aluminum nitrate is 28.34/52.52, and the quality of nitrate of lime is 0.01-0.12g/ml with the ratio of aqueous citric acid solution volume; Add polyglycol surfactants then, the quality of polyethylene glycol is 2.5mg/ml with the ratio of aqueous citric acid solution volume; The control bath temperature obtains settled solution with the rotating speed continuous stirring of 200-500r/min until dissolving under 70-80 ℃ of condition; Add ethylene glycol in above-mentioned solution, the addition of ethylene glycol is 0.25-0.6/1 with the ratio of the volume of aqueous citric acid solution; , in 90 ℃ of environment, leave standstill then and formed calcium aluminium salt gel in 24 hours until forming calcium aluminium salt sol with the rotating speed continuous stirring of 200-500r/min; Calcium aluminium salt gel is heated to 350-400 ℃ and be incubated 1-2 hour in air atmosphere, makes it form blocks of solid; Blocks of solid is ground to form the particulate of particle diameter less than 0.15mm; Place uncovered quartz or ceramic vessel to put in the sealed reactor particulate after grinding, the feeding flow velocity is 50-100cm again
3The oxygen of/min is under the condition of 0.11-0.13MPa at oxygen atmosphere pressure, is heated to 900-1150 ℃ and be incubated 8-10 hour with 5-10 ℃ of/minute programming rate, and obtaining particle diameter is the polycrystal nano calcium aluminum oxide C12A7-O of 10-200nm
-
2. polycrystal nano calcium aluminum oxide C12A7-O as claimed in claim 1
-Purposes as anti-biotic material is characterized in that, load weight is more than or equal to 0.005g/cm on the unit are of polycrystal nano calcium aluminum oxide in support materials
2The time, be 100% to staphylococcus aureus, 1 hour killing rate of colon bacillus, be 96% to 1 hour killing rate of bacillus subtilis black variety gemma effect.
3. polycrystal nano calcium aluminum oxide C12A7-O as claimed in claim 1
-Purposes as anti-biotic material is characterized in that, when polycrystal nano calcium aluminum oxide load weight on the support materials unit are is 0.0025g/cm
2-0.005g/cm
2The time, be 99-100% to staphylococcus aureus, 1 hour killing rate of colon bacillus effect, be 91-96% to 1 hour killing rate of bacillus subtilis black variety gemma effect.
4. polycrystal nano calcium aluminum oxide C12A7-O as claimed in claim 1
-Purposes as anti-biotic material is characterized in that, when polycrystal nano calcium aluminum oxide load weight on the support materials unit are is 0.0005g/cm
2-0.0025g/cm
2The time, be 98-99% to 1 hour killing rate of staphylococcus aureus effect, be 84-99% to 1 hour killing rate of colon bacillus effect, be 29-91% to 1 hour killing rate of bacillus subtilis black variety gemma effect.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN200910116326XA CN101518259B (en) | 2009-03-11 | 2009-03-11 | Antibacterial application of polycrystalline nanometer calcium-aluminum oxide |
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| WO2018014144A1 (en) * | 2016-07-22 | 2018-01-25 | Universidad De Santiago De Chile | Polymer comprising cao nanoparticles for food packaging |
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| GB0909030D0 (en) * | 2009-05-26 | 2009-07-01 | Intrinsiq Materials Ltd | Antibacterial composition |
| CN108217775B (en) * | 2018-02-05 | 2022-04-29 | 合肥市联任科技有限公司 | Chlorine-containing wastewater treatment agent and preparation method thereof |
| CL2019002565A1 (en) * | 2019-09-09 | 2019-11-29 | Univ Santiago Chile | Nanoparticles of calcium oxide and polymeric nanocomposites that comprise them, method of obtaining from natural solid food by-products / discards rich in calcium carbonate and method of preparing polymeric nanocomposites, and use as antimicrobial in films for food packaging or coatings of different surfaces |
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| CN101306370A (en) * | 2008-06-03 | 2008-11-19 | 中国科学技术大学 | Mixed oxide catalyst and use thereof in steam reforming bio-oil hydrogen making |
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| CN101306370A (en) * | 2008-06-03 | 2008-11-19 | 中国科学技术大学 | Mixed oxide catalyst and use thereof in steam reforming bio-oil hydrogen making |
Non-Patent Citations (2)
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| Quanxin Li,et al..High-intensity atomic oxygen radical anion emission mechanism from 12CaO.7Al2O3 crystal surface.《Surface Science》.2003,第527卷第100-112页. * |
| Wang Lian,et al..Effect of Atomic Oxygen Radical Anion on Escherichia coli Cells.《Progress in Biochemistry and Biophysics》.2007,第34卷(第12期),第1288-1295页. * |
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| WO2018014144A1 (en) * | 2016-07-22 | 2018-01-25 | Universidad De Santiago De Chile | Polymer comprising cao nanoparticles for food packaging |
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